(2,2′-Bipyridine-6,6′-dicarboxyl­ato-κ3N,N′,O6)(6′-carb­oxy-2,2′-bipyridine-6-carboxyl­ato-κ3N,N′,O6)rhodium(III)

Wang, H.; Gu, X.; Zhang, B.; Su, H.; Hu, M.

doi:10.1107/S1600536812004850

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m290-m291

doi:10.1107/S1600536812004850

Open

access

(2,2′-Bipyridine-6,6′-dicarboxylato-κ³N,N′,O⁶)(6′-carboxy-2,2′-bipyridine-6-carboxylato-κ³N,N′,O⁶)rhodium(III)

Huimin Wang,^a Xiaojun Gu,^b Bingbing Zhang,^a Haiquan Su ^a,^b ^* and Ming Hu ^b

^aCollege of Life Sciences, Inner Mongolia University, Hohhot 010021, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, People's Republic of China
^*Correspondence e-mail: haiquansu@yahoo.com

(Received 18 January 2012; accepted 4 February 2012; online 17 February 2012)

The Rh^III ion in the title compound, [Rh(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)], is coordinated by four N atoms and two O atoms from two chelating ligands L and HL (H₂L = 2,2′-bipyridine-6,6′-dicarboxylic acid) to form a distorted octahedral geometry. Face-to-face π-stacking interactions are observed between inversion-related pyridine rings, with a centroid-to-centroid distance of 3.581 (1) Å [the perpendicular distance between the rings is 3.3980 (7) Å]. Intermolecular O—H⋯O hydrogen bonds link adjacent molecules into one-dimensional supramolecular chains along the c axis, while several intermolecular C—H⋯O interactions are also observed.

Related literature

For structures and photophysical properties of Ln^III (Ln is a lanthanide) complexes with the title ligand, see: Bünzli et al. (2000 ). For Rh complexes with pyridyl triazole ligands, see: Burke et al. (2004 ). For an Mn–Rh coordination polymer with the 2-methylpyrazine-5-carboxylic acid ligand, see: Chapman et al. (2002 ). For a catena-poly diaqua Cd^II complex with the title ligand, see: Knight et al. (2006 ). For a review reporting the properties of coordination polymer networks via O and N atoms, see: Robin & Fromm (2006 ). For the structures and thermal properties of five Ln complexes with the title ligand, see: Wang et al. (2010 ). For a related Ni^II complex with the title ligand, see: Wang et al. (2009 ).

Experimental

Crystal data

[Rh(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]
M_r = 588.29
Monoclinic, P 2₁ /c
a = 9.3308 (4) Å
b = 13.6186 (6) Å
c = 16.9974 (8) Å
β = 100.696 (1)°
V = 2122.37 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 296 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
15424 measured reflections
5269 independent reflections
4714 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.03
5269 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Rh1—N1	1.9529 (13)
Rh1—N4	1.9571 (14)
Rh1—O1	2.0226 (12)
Rh1—O5	2.0316 (13)
Rh1—N3	2.0689 (15)
Rh1—N2	2.0808 (14)

N2—C6—C5—N1	−2.1 (2)
N4—C15—C16—N3	−1.8 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O7ⁱ	0.82	1.64	2.443 (2)	168
C2—H2⋯O6ⁱⁱ	0.93	2.51	3.326 (2)	147
C4—H4A⋯O5ⁱⁱⁱ	0.93	2.54	3.341 (2)	145
C7—H7⋯O5ⁱⁱⁱ	0.93	2.51	3.304 (2)	143
C9—H9⋯O8^iv	0.93	2.36	3.097 (2)	136
C12—H12⋯O1^v	0.93	2.59	3.194 (2)	123
C17—H17⋯O7^vi	0.93	2.42	3.148 (2)	136
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z; (iv) -x+1, -y, -z; (v) -x, -y+1, -z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004850/zq2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004850/zq2151Isup2.hkl

checkCIF report

Comment top

Thanks to diverse coordination modes and aromatic cores, many multidentate ligands containing N- or O-donors, such as pyridine-2,6-dicarboxylic acid, 2,2'-dipyridine-4,4'-dicarboxylic acid and 2,2'-dipyridine-5,5'-dicarboxylic acid, have been widely used in metal–organic coordination chemistry (Robin & Fromm, 2006; Wang et al., 2009). However, the study of complexes with the title ligand (H₂L = 2,2'-bipyridine-6,6'-dicarboxylic acid) is still rare. Some X-ray crystal structures constructed from the title ligand and metal ions, such as [Ln₂L₃(H₂O)₃].xH₂O (x = 1, Ln = Eu, Tb; x = 0, Ln = Gd) (Bünzli et al., 2000), [Ln₃L₄(HL)(H₂O)₂].12H₂O (Ln = Ce, Nd, Pr) (Wang et al., 2010), [Ln₂L₃(H₂O)₃].3H₂O (Ln = Er, Tm) (Wang et al., 2010), [NiL₂].4H₂O (Wang et al., 2009) and [CdL]_n.2nH₂O (Knight et al., 2006), have been investigated previously. Here we isolated a new compound constructed from the title ligand and rhodium(III) under hydrothermal conditions. A careful literature survey showed that it is the first compound constructed from rhodium(III) and the title ligand.

The structure of the title compound (Fig. 1) shows that the six-coordinated Rh^III atom is surrounded by four N atoms and two O atoms from the two chelated ligands to form a distorted octahedral geometry. The Rh—N bond lengths are in the range of 1.9529 (13)–2.0808 (14) Å and the Rh—O bond lengths are 2.0226 (12) and 2.0316 (13) Å (Table 1), which are comparable to other distances reported in Rh^III complexes (Burke et al., 2004; Chapman et al., 2002). The coordinated bipyridine fragments are nearly coplanar [see torsion angles of 2.1 (2) and 1.8 (2)° in Table 1].

Face-to-face π-stacking interactions between inversion-related pyridine rings with Cg1···Cg2ⁱⁱ distance of 3.581 (1) Å (the perpendicular distance between the rings is 3.3980 (7) Å) are observed in the crystal structure: Cg1 and Cg2 are the centroids of the pyridine rings (N1,C1–C5) and (N2,C6–C10), respectively (symmetry code: ii = -x, -y, -z). A similar situation of face-to-face π-stacking interactions was observed in our early work (Wang et al., 2009).

The one-dimensional chain structure of the title compound via hydrogen bonds is illustrated in Fig. 2. The hydrogen-bond donor O4 is connected to the acceptor O7 from the adjacent molecule to form one-dimensional infinite chains along the c-axis (O4—H4···O7ⁱ = 1.64 Å, i = x, -y + 1/2, z - 1/2, Table 2). Several intermolecular C—H···O interactions contribute to stabilize the crystal structure.

Related literature top

For structures and photophysical properties of Ln^III complexes with the title ligand, see: Bünzli et al. (2000). For Rh complexes with pyridyl triazole ligands, see: Burke et al. (2004). For an Mn–Rh coordination polymer with the 2-methylpyrazine-5-carboxylic acid ligand, see: Chapman et al. (2002). For a catena-poly diaqua Cd^II complex with the title ligand, see: Knight et al. (2006). For a review reporting the properties of coordination polymer networks via O and N atoms, see: Robin & Fromm (2006). For the structures and thermal properties of five Ln^III complexes with the title ligand, see: Wang et al. (2010). For a related Ni^II complex with the title ligand, see: Wang et al. (2009).

Experimental top

The title compound was obtained by the reaction of the mixture of RhCl₃ and 2,2'-dipyridine-6,6'-dicarboxylic acid in a molar ratio of 1:3 and 10 ml of water under hydrothermal conditions (at 433 K for 3 d and cooled to room temperature with a 3°C h^-1 rate). The orange block crystals were washed with water (yield: 40%).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. The one-dimensional chain structure of the title compound via hydrogen bonds along the c-axis.

(2,2'-Bipyridine-6,6'-dicarboxylato- κ³N,N',O⁶)(6'-carboxy-2,2'-bipyridine-6-carboxylato- κ³N,N',O⁶)rhodium(III) top

Crystal data top

[Rh(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]	Z = 4
M_r = 588.29	F(000) = 1176
Monoclinic, P2₁/c	D_x = 1.841 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3308 (4) Å	µ = 0.87 mm⁻¹
b = 13.6186 (6) Å	T = 296 K
c = 16.9974 (8) Å	Block, orange
β = 100.696 (1)°	0.2 × 0.2 × 0.2 mm
V = 2122.37 (16) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4714 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 28.3°, θ_min = 1.9°
ϕ and ω scans	h = −10→12
15424 measured reflections	k = −17→18
5269 independent reflections	l = −22→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0317P)² + 1.1072P] where P = (F_o² + 2F_c²)/3
5269 reflections	(Δ/σ)_max < 0.001
335 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Rh(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]	V = 2122.37 (16) Å³
M_r = 588.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3308 (4) Å	µ = 0.87 mm⁻¹
b = 13.6186 (6) Å	T = 296 K
c = 16.9974 (8) Å	0.2 × 0.2 × 0.2 mm
β = 100.696 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4714 reflections with I > 2σ(I)
15424 measured reflections	R_int = 0.017
5269 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.03	Δρ_max = 0.42 e Å⁻³
5269 reflections	Δρ_min = −0.58 e Å⁻³
335 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Rh1	0.159112 (14)	0.237745 (9)	0.067212 (7)	0.02121 (5)
N1	0.08891 (15)	0.12682 (10)	0.12226 (8)	0.0225 (3)
N2	0.24130 (15)	0.12072 (10)	0.01055 (8)	0.0237 (3)
O5	−0.02277 (15)	0.23972 (9)	−0.01957 (8)	0.0298 (3)
N4	0.19640 (17)	0.35997 (10)	0.01389 (9)	0.0265 (3)
C6	0.20550 (18)	0.03125 (12)	0.03847 (10)	0.0250 (3)
C5	0.11551 (18)	0.03481 (12)	0.10163 (10)	0.0241 (3)
O1	0.05205 (14)	0.31499 (9)	0.13993 (8)	0.0287 (3)
N3	0.35387 (16)	0.27865 (11)	0.13906 (9)	0.0261 (3)
O4	0.26900 (19)	0.24099 (12)	−0.14737 (10)	0.0473 (4)
H4	0.3000	0.2889	−0.1681	0.071*
C4	0.0559 (2)	−0.04235 (13)	0.13826 (11)	0.0298 (4)
H4A	0.0739	−0.1071	0.1258	0.036*
C21	−0.0203 (2)	0.25889 (13)	0.18174 (12)	0.0297 (4)
C11	0.0918 (2)	0.38968 (13)	−0.04605 (11)	0.0299 (4)
O7	0.32750 (17)	0.11501 (10)	0.27890 (8)	0.0415 (3)
C20	0.4329 (2)	0.23263 (13)	0.20224 (11)	0.0297 (4)
O8	0.42615 (17)	0.06416 (10)	0.17725 (9)	0.0409 (3)
C24	0.3925 (2)	0.12843 (13)	0.21996 (11)	0.0299 (4)
O3	0.4556 (2)	0.26903 (12)	−0.04658 (11)	0.0534 (4)
O6	−0.13732 (17)	0.33511 (12)	−0.11836 (9)	0.0457 (4)
C1	0.00247 (19)	0.14967 (13)	0.17412 (10)	0.0257 (3)
C15	0.3070 (2)	0.41706 (13)	0.04922 (11)	0.0305 (4)
C3	−0.0313 (2)	−0.02061 (14)	0.19393 (11)	0.0330 (4)
H3	−0.0709	−0.0715	0.2195	0.040*
C7	0.2492 (2)	−0.05583 (13)	0.00854 (11)	0.0314 (4)
H7	0.2245	−0.1157	0.0287	0.038*
C9	0.3635 (2)	0.03691 (15)	−0.08131 (12)	0.0344 (4)
H9	0.4161	0.0403	−0.1227	0.041*
C16	0.3976 (2)	0.37045 (13)	0.11932 (12)	0.0308 (4)
C23	−0.0336 (2)	0.31820 (14)	−0.06556 (11)	0.0317 (4)
C8	0.3306 (2)	−0.05271 (15)	−0.05210 (12)	0.0349 (4)
H8	0.3623	−0.1104	−0.0726	0.042*
O2	−0.10279 (18)	0.29013 (11)	0.22277 (11)	0.0498 (4)
C18	0.5979 (2)	0.36721 (17)	0.22862 (14)	0.0457 (5)
H18	0.6798	0.3969	0.2588	0.055*
C2	−0.0601 (2)	0.07623 (14)	0.21197 (11)	0.0320 (4)
H2	−0.1199	0.0909	0.2485	0.038*
C13	0.2164 (3)	0.54139 (15)	−0.04621 (14)	0.0434 (5)
H13	0.2255	0.6030	−0.0684	0.052*
C10	0.31789 (19)	0.12252 (13)	−0.04881 (11)	0.0277 (3)
C14	0.3194 (2)	0.51125 (14)	0.01885 (14)	0.0399 (5)
H14	0.3949	0.5527	0.0417	0.048*
C12	0.1004 (2)	0.48196 (14)	−0.07888 (12)	0.0386 (4)
H12	0.0303	0.5034	−0.1216	0.046*
C19	0.5562 (2)	0.27527 (16)	0.24857 (14)	0.0419 (5)
H19	0.6092	0.2420	0.2922	0.050*
C22	0.3551 (2)	0.22076 (15)	−0.08135 (11)	0.0321 (4)
C17	0.5179 (2)	0.41533 (15)	0.16363 (13)	0.0400 (5)
H17	0.5452	0.4778	0.1499	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.02553 (8)	0.01557 (7)	0.02292 (7)	−0.00143 (4)	0.00549 (5)	−0.00021 (4)
N1	0.0264 (7)	0.0176 (6)	0.0235 (7)	−0.0014 (5)	0.0043 (5)	0.0010 (5)
N2	0.0262 (7)	0.0203 (6)	0.0246 (7)	−0.0007 (5)	0.0046 (6)	−0.0018 (5)
O5	0.0323 (7)	0.0257 (6)	0.0296 (7)	−0.0020 (5)	0.0010 (5)	0.0006 (5)
N4	0.0340 (8)	0.0190 (7)	0.0284 (7)	−0.0008 (6)	0.0108 (6)	0.0010 (5)
C6	0.0266 (8)	0.0215 (8)	0.0258 (8)	−0.0009 (6)	0.0021 (7)	−0.0012 (6)
C5	0.0275 (8)	0.0195 (7)	0.0240 (8)	−0.0005 (6)	0.0014 (6)	−0.0003 (6)
O1	0.0349 (7)	0.0197 (6)	0.0336 (7)	0.0008 (5)	0.0119 (5)	−0.0026 (5)
N3	0.0277 (7)	0.0221 (7)	0.0289 (7)	−0.0024 (6)	0.0063 (6)	−0.0041 (6)
O4	0.0565 (10)	0.0437 (9)	0.0410 (9)	−0.0150 (7)	0.0075 (7)	0.0115 (6)
C4	0.0366 (10)	0.0196 (8)	0.0317 (9)	−0.0019 (7)	0.0019 (7)	0.0027 (7)
C21	0.0312 (9)	0.0253 (8)	0.0332 (9)	−0.0002 (7)	0.0079 (7)	−0.0035 (7)
C11	0.0402 (10)	0.0248 (8)	0.0268 (9)	0.0052 (7)	0.0114 (7)	0.0022 (7)
O7	0.0612 (9)	0.0309 (7)	0.0357 (7)	0.0079 (7)	0.0174 (7)	0.0000 (6)
C20	0.0286 (9)	0.0299 (9)	0.0299 (9)	0.0033 (7)	0.0038 (7)	−0.0067 (7)
O8	0.0523 (9)	0.0313 (7)	0.0405 (8)	0.0085 (6)	0.0122 (7)	−0.0078 (6)
C24	0.0309 (9)	0.0282 (9)	0.0279 (9)	0.0074 (7)	−0.0017 (7)	−0.0018 (7)
O3	0.0542 (10)	0.0489 (10)	0.0556 (10)	−0.0211 (8)	0.0065 (8)	−0.0042 (8)
O6	0.0470 (9)	0.0529 (9)	0.0332 (7)	0.0040 (7)	−0.0036 (6)	0.0070 (7)
C1	0.0287 (8)	0.0245 (8)	0.0241 (8)	−0.0007 (6)	0.0054 (7)	−0.0010 (6)
C15	0.0354 (10)	0.0216 (8)	0.0375 (10)	−0.0036 (7)	0.0147 (8)	−0.0020 (7)
C3	0.0392 (10)	0.0278 (9)	0.0321 (9)	−0.0053 (7)	0.0072 (8)	0.0079 (7)
C7	0.0356 (10)	0.0226 (8)	0.0348 (10)	0.0005 (7)	0.0036 (8)	−0.0027 (7)
C9	0.0336 (10)	0.0385 (11)	0.0330 (10)	0.0039 (8)	0.0109 (8)	−0.0068 (8)
C16	0.0324 (9)	0.0247 (8)	0.0374 (10)	−0.0050 (7)	0.0116 (8)	−0.0067 (7)
C23	0.0390 (10)	0.0301 (9)	0.0266 (9)	0.0047 (8)	0.0080 (8)	−0.0009 (7)
C8	0.0359 (10)	0.0306 (10)	0.0379 (10)	0.0073 (8)	0.0057 (8)	−0.0094 (8)
O2	0.0586 (10)	0.0346 (8)	0.0667 (11)	0.0002 (7)	0.0390 (9)	−0.0092 (7)
C18	0.0322 (10)	0.0469 (13)	0.0547 (13)	−0.0081 (9)	−0.0003 (9)	−0.0187 (10)
C2	0.0367 (10)	0.0336 (9)	0.0275 (9)	−0.0027 (8)	0.0109 (7)	0.0024 (7)
C13	0.0599 (14)	0.0240 (9)	0.0528 (13)	0.0031 (9)	0.0273 (11)	0.0111 (8)
C10	0.0272 (8)	0.0289 (9)	0.0272 (8)	−0.0008 (7)	0.0054 (7)	−0.0024 (7)
C14	0.0459 (12)	0.0233 (9)	0.0554 (13)	−0.0066 (8)	0.0224 (10)	0.0000 (8)
C12	0.0537 (12)	0.0296 (10)	0.0354 (10)	0.0080 (9)	0.0159 (9)	0.0084 (8)
C19	0.0343 (10)	0.0438 (12)	0.0427 (12)	0.0021 (9)	−0.0055 (9)	−0.0096 (9)
C22	0.0350 (10)	0.0329 (10)	0.0328 (10)	−0.0022 (7)	0.0179 (8)	−0.0034 (7)
C17	0.0366 (11)	0.0323 (10)	0.0518 (12)	−0.0106 (8)	0.0101 (9)	−0.0113 (9)

Geometric parameters (Å, º) top

Rh1—N1	1.9529 (13)	C20—C24	1.513 (3)
Rh1—N4	1.9571 (14)	O8—C24	1.215 (2)
Rh1—O1	2.0226 (12)	O3—C22	1.206 (3)
Rh1—O5	2.0316 (13)	O6—C23	1.213 (2)
Rh1—N3	2.0689 (15)	C1—C2	1.377 (2)
Rh1—N2	2.0808 (14)	C15—C14	1.396 (3)
N1—C5	1.337 (2)	C15—C16	1.471 (3)
N1—C1	1.337 (2)	C3—C2	1.391 (3)
N2—C10	1.341 (2)	C3—H3	0.9300
N2—C6	1.371 (2)	C7—C8	1.390 (3)
O5—C23	1.317 (2)	C7—H7	0.9300
N4—C11	1.336 (2)	C9—C8	1.374 (3)
N4—C15	1.342 (2)	C9—C10	1.390 (3)
C6—C7	1.382 (2)	C9—H9	0.9300
C6—C5	1.481 (2)	C16—C17	1.374 (3)
C5—C4	1.389 (2)	C8—H8	0.9300
O1—C21	1.313 (2)	C18—C19	1.372 (3)
N3—C20	1.340 (2)	C18—C17	1.379 (3)
N3—C16	1.376 (2)	C18—H18	0.9300
O4—C22	1.283 (3)	C2—H2	0.9300
O4—H4	0.8200	C13—C12	1.382 (3)
C4—C3	1.389 (3)	C13—C14	1.386 (3)
C4—H4A	0.9300	C13—H13	0.9300
C21—O2	1.208 (2)	C10—C22	1.513 (3)
C21—C1	1.512 (2)	C14—H14	0.9300
C11—C12	1.383 (3)	C12—H12	0.9300
C11—C23	1.511 (3)	C19—H19	0.9300
O7—C24	1.277 (2)	C17—H17	0.9300
C20—C19	1.394 (3)

N1—Rh1—N4	169.74 (6)	N1—C1—C2	119.94 (16)
N1—Rh1—O1	82.06 (5)	N1—C1—C21	113.40 (15)
N4—Rh1—O1	89.49 (5)	C2—C1—C21	126.61 (16)
N1—Rh1—O5	92.80 (5)	N4—C15—C14	118.48 (18)
N4—Rh1—O5	81.31 (6)	N4—C15—C16	113.04 (15)
O1—Rh1—O5	89.77 (5)	C14—C15—C16	128.44 (18)
N1—Rh1—N3	105.16 (6)	C4—C3—C2	120.91 (17)
N4—Rh1—N3	80.34 (6)	C4—C3—H3	119.5
O1—Rh1—N3	88.77 (5)	C2—C3—H3	119.5
O5—Rh1—N3	161.60 (5)	C6—C7—C8	119.09 (18)
N1—Rh1—N2	79.31 (6)	C6—C7—H7	120.5
N4—Rh1—N2	108.94 (6)	C8—C7—H7	120.5
O1—Rh1—N2	161.35 (5)	C8—C9—C10	119.73 (18)
O5—Rh1—N2	90.23 (5)	C8—C9—H9	120.1
N3—Rh1—N2	96.93 (6)	C10—C9—H9	120.1
C5—N1—C1	123.71 (15)	C17—C16—N3	121.32 (19)
C5—N1—Rh1	120.29 (12)	C17—C16—C15	122.71 (17)
C1—N1—Rh1	115.65 (11)	N3—C16—C15	115.96 (16)
C10—N2—C6	118.36 (15)	O6—C23—O5	123.79 (19)
C10—N2—Rh1	128.91 (12)	O6—C23—C11	121.25 (18)
C6—N2—Rh1	112.71 (11)	O5—C23—C11	114.92 (16)
C23—O5—Rh1	113.81 (12)	C9—C8—C7	119.00 (17)
C11—N4—C15	123.93 (15)	C9—C8—H8	120.5
C11—N4—Rh1	116.31 (12)	C7—C8—H8	120.5
C15—N4—Rh1	118.27 (12)	C19—C18—C17	119.67 (19)
N2—C6—C7	121.85 (16)	C19—C18—H18	120.2
N2—C6—C5	115.40 (14)	C17—C18—H18	120.2
C7—C6—C5	122.74 (15)	C1—C2—C3	118.00 (17)
N1—C5—C4	118.83 (16)	C1—C2—H2	121.0
N1—C5—C6	112.24 (14)	C3—C2—H2	121.0
C4—C5—C6	128.90 (15)	C12—C13—C14	121.48 (18)
C21—O1—Rh1	112.97 (10)	C12—C13—H13	119.3
C20—N3—C16	118.43 (16)	C14—C13—H13	119.3
C20—N3—Rh1	129.77 (12)	N2—C10—C9	121.95 (17)
C16—N3—Rh1	111.63 (12)	N2—C10—C22	118.83 (16)
C22—O4—H4	109.5	C9—C10—C22	119.23 (16)
C5—C4—C3	118.54 (16)	C13—C14—C15	118.33 (19)
C5—C4—H4A	120.7	C13—C14—H14	120.8
C3—C4—H4A	120.7	C15—C14—H14	120.8
O2—C21—O1	123.68 (17)	C13—C12—C11	118.02 (19)
O2—C21—C1	120.73 (17)	C13—C12—H12	121.0
O1—C21—C1	115.58 (15)	C11—C12—H12	121.0
N4—C11—C12	119.57 (18)	C18—C19—C20	118.9 (2)
N4—C11—C23	113.49 (15)	C18—C19—H19	120.6
C12—C11—C23	126.69 (18)	C20—C19—H19	120.6
N3—C20—C19	122.11 (18)	O3—C22—O4	128.0 (2)
N3—C20—C24	118.53 (16)	O3—C22—C10	120.88 (19)
C19—C20—C24	119.22 (18)	O4—C22—C10	111.14 (16)
O8—C24—O7	125.35 (18)	C16—C17—C18	119.59 (19)
O8—C24—C20	117.09 (17)	C16—C17—H17	120.2
O7—C24—C20	117.56 (16)	C18—C17—H17	120.2

N4—Rh1—N1—C5	142.4 (3)	Rh1—N4—C11—C12	170.67 (14)
O1—Rh1—N1—C5	177.26 (13)	C15—N4—C11—C23	−169.87 (16)
O5—Rh1—N1—C5	87.88 (13)	Rh1—N4—C11—C23	−4.10 (19)
N3—Rh1—N1—C5	−96.19 (13)	C16—N3—C20—C19	0.7 (3)
N2—Rh1—N1—C5	−1.83 (12)	Rh1—N3—C20—C19	−174.12 (15)
N4—Rh1—N1—C1	−31.0 (4)	C16—N3—C20—C24	−174.99 (16)
O1—Rh1—N1—C1	3.86 (12)	Rh1—N3—C20—C24	10.2 (2)
O5—Rh1—N1—C1	−85.52 (12)	N3—C20—C24—O8	75.6 (2)
N3—Rh1—N1—C1	90.41 (13)	C19—C20—C24—O8	−100.2 (2)
N2—Rh1—N1—C1	−175.23 (13)	N3—C20—C24—O7	−105.1 (2)
N1—Rh1—N2—C10	178.45 (16)	C19—C20—C24—O7	79.0 (2)
N4—Rh1—N2—C10	4.76 (16)	C5—N1—C1—C2	2.6 (3)
O1—Rh1—N2—C10	175.62 (15)	Rh1—N1—C1—C2	175.79 (13)
O5—Rh1—N2—C10	85.64 (15)	C5—N1—C1—C21	−174.92 (15)
N3—Rh1—N2—C10	−77.37 (15)	Rh1—N1—C1—C21	−1.77 (19)
N1—Rh1—N2—C6	0.49 (11)	O2—C21—C1—N1	175.54 (19)
N4—Rh1—N2—C6	−173.19 (11)	O1—C21—C1—N1	−3.0 (2)
O1—Rh1—N2—C6	−2.3 (2)	O2—C21—C1—C2	−1.8 (3)
O5—Rh1—N2—C6	−92.31 (12)	O1—C21—C1—C2	179.66 (17)
N3—Rh1—N2—C6	104.68 (12)	C11—N4—C15—C14	−4.0 (3)
N1—Rh1—O5—C23	168.90 (13)	Rh1—N4—C15—C14	−169.55 (14)
N4—Rh1—O5—C23	−2.66 (12)	C11—N4—C15—C16	173.52 (16)
O1—Rh1—O5—C23	86.86 (12)	Rh1—N4—C15—C16	8.0 (2)
N3—Rh1—O5—C23	1.4 (2)	C5—C4—C3—C2	0.9 (3)
N2—Rh1—O5—C23	−111.79 (13)	N2—C6—C7—C8	−0.6 (3)
N1—Rh1—N4—C11	−51.6 (4)	C5—C6—C7—C8	178.45 (16)
O1—Rh1—N4—C11	−86.07 (13)	C20—N3—C16—C17	−1.0 (3)
O5—Rh1—N4—C11	3.78 (12)	Rh1—N3—C16—C17	174.67 (15)
N3—Rh1—N4—C11	−174.92 (13)	C20—N3—C16—C15	179.72 (16)
N2—Rh1—N4—C11	91.02 (13)	Rh1—N3—C16—C15	−4.57 (19)
N1—Rh1—N4—C15	115.0 (3)	N4—C15—C16—C17	178.97 (17)
O1—Rh1—N4—C15	80.54 (13)	C14—C15—C16—C17	−3.8 (3)
O5—Rh1—N4—C15	170.39 (14)	N4—C15—C16—N3	−1.8 (2)
N3—Rh1—N4—C15	−8.30 (13)	C14—C15—C16—N3	175.46 (18)
N2—Rh1—N4—C15	−102.37 (13)	Rh1—O5—C23—O6	−176.56 (16)
C10—N2—C6—C7	1.6 (2)	Rh1—O5—C23—C11	1.25 (19)
Rh1—N2—C6—C7	179.84 (14)	N4—C11—C23—O6	179.66 (17)
C10—N2—C6—C5	−177.49 (15)	C12—C11—C23—O6	5.3 (3)
Rh1—N2—C6—C5	0.70 (18)	N4—C11—C23—O5	1.8 (2)
C1—N1—C5—C4	−2.9 (3)	C12—C11—C23—O5	−172.54 (18)
Rh1—N1—C5—C4	−175.79 (12)	C10—C9—C8—C7	1.4 (3)
C1—N1—C5—C6	175.50 (15)	C6—C7—C8—C9	−0.9 (3)
Rh1—N1—C5—C6	2.7 (2)	N1—C1—C2—C3	−0.5 (3)
N2—C6—C5—N1	−2.1 (2)	C21—C1—C2—C3	176.71 (18)
C7—C6—C5—N1	178.79 (16)	C4—C3—C2—C1	−1.2 (3)
N2—C6—C5—C4	176.16 (17)	C6—N2—C10—C9	−1.2 (3)
C7—C6—C5—C4	−3.0 (3)	Rh1—N2—C10—C9	−179.03 (13)
N1—Rh1—O1—C21	−5.47 (13)	C6—N2—C10—C22	178.66 (15)
N4—Rh1—O1—C21	168.69 (13)	Rh1—N2—C10—C22	0.8 (2)
O5—Rh1—O1—C21	87.39 (13)	C8—C9—C10—N2	−0.3 (3)
N3—Rh1—O1—C21	−110.96 (13)	C8—C9—C10—C22	179.85 (18)
N2—Rh1—O1—C21	−2.7 (2)	C12—C13—C14—C15	2.5 (3)
N1—Rh1—N3—C20	10.65 (17)	N4—C15—C14—C13	0.3 (3)
N4—Rh1—N3—C20	−178.22 (16)	C16—C15—C14—C13	−176.87 (19)
O1—Rh1—N3—C20	92.09 (16)	C14—C13—C12—C11	−1.7 (3)
O5—Rh1—N3—C20	177.68 (16)	N4—C11—C12—C13	−1.9 (3)
N2—Rh1—N3—C20	−70.10 (16)	C23—C11—C12—C13	172.14 (18)
N1—Rh1—N3—C16	−164.44 (12)	C17—C18—C19—C20	0.0 (3)
N4—Rh1—N3—C16	6.69 (12)	N3—C20—C19—C18	−0.2 (3)
O1—Rh1—N3—C16	−83.00 (12)	C24—C20—C19—C18	175.48 (19)
O5—Rh1—N3—C16	2.6 (2)	N2—C10—C22—O3	79.9 (2)
N2—Rh1—N3—C16	114.81 (12)	C9—C10—C22—O3	−100.3 (2)
N1—C5—C4—C3	1.1 (3)	N2—C10—C22—O4	−100.8 (2)
C6—C5—C4—C3	−177.02 (17)	C9—C10—C22—O4	79.0 (2)
Rh1—O1—C21—O2	−172.48 (18)	N3—C16—C17—C18	0.9 (3)
Rh1—O1—C21—C1	6.0 (2)	C15—C16—C17—C18	−179.95 (19)
C15—N4—C11—C12	4.9 (3)	C19—C18—C17—C16	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O7ⁱ	0.82	1.64	2.443 (2)	168
C2—H2···O6ⁱⁱ	0.93	2.51	3.326 (2)	147
C4—H4A···O5ⁱⁱⁱ	0.93	2.54	3.341 (2)	145
C7—H7···O5ⁱⁱⁱ	0.93	2.51	3.304 (2)	143
C9—H9···O8^iv	0.93	2.36	3.097 (2)	136
C12—H12···O1^v	0.93	2.59	3.194 (2)	123
C17—H17···O7^vi	0.93	2.42	3.148 (2)	136

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z; (iv) −x+1, −y, −z; (v) −x, −y+1, −z; (vi) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Rh(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]
M_r	588.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.3308 (4), 13.6186 (6), 16.9974 (8)
β (°)	100.696 (1)
V (Å³)	2122.37 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15424, 5269, 4714
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.03
No. of reflections	5269
No. of parameters	335
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.58

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top

Rh1—N1	1.9529 (13)	Rh1—O5	2.0316 (13)
Rh1—N4	1.9571 (14)	Rh1—N3	2.0689 (15)
Rh1—O1	2.0226 (12)	Rh1—N2	2.0808 (14)

N1—Rh1—N4	169.74 (6)	O1—Rh1—N3	88.77 (5)
N1—Rh1—O1	82.06 (5)	O5—Rh1—N3	161.60 (5)
N4—Rh1—O1	89.49 (5)	N1—Rh1—N2	79.31 (6)
N1—Rh1—O5	92.80 (5)	N4—Rh1—N2	108.94 (6)
N4—Rh1—O5	81.31 (6)	O1—Rh1—N2	161.35 (5)
O1—Rh1—O5	89.77 (5)	O5—Rh1—N2	90.23 (5)
N1—Rh1—N3	105.16 (6)	N3—Rh1—N2	96.93 (6)
N4—Rh1—N3	80.34 (6)

N2—C6—C5—N1	−2.1 (2)	N4—C15—C16—N3	−1.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O7ⁱ	0.82	1.64	2.443 (2)	167.9
C2—H2···O6ⁱⁱ	0.93	2.51	3.326 (2)	146.7
C4—H4A···O5ⁱⁱⁱ	0.93	2.54	3.341 (2)	145.1
C7—H7···O5ⁱⁱⁱ	0.93	2.51	3.304 (2)	143.2
C9—H9···O8^iv	0.93	2.36	3.097 (2)	136.3
C12—H12···O1^v	0.93	2.59	3.194 (2)	122.9
C17—H17···O7^vi	0.93	2.42	3.148 (2)	135.5

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z; (iv) −x+1, −y, −z; (v) −x, −y+1, −z; (vi) −x+1, y+1/2, −z+1/2.

Acknowledgements

This project was supported by the National Natural Science Foundation of China (grant No. 21166014) and a Key Grant of the Inner Mongolia Natural Science Foundation of China (grant No. 2010ZD01).

References

Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bünzli, J.-C. G., Charbonnière, L. J. & Ziessel, R. F. (2000). J. Chem. Soc. Dalton Trans. pp. 1917–1923. Google Scholar
Burke, H. M., Gallagher, J. F., Indelli, M. T. & Vos, J. G. (2004). Inorg. Chim. Acta, 357, 2989–3000. Web of Science CSD CrossRef CAS Google Scholar
Chapman, C. T., Ciurtin, D. M., Smith, M. D. & zur Loye, H.-C. (2002). Solid State Sci. 4, 1187–1191. Web of Science CSD CrossRef CAS Google Scholar
Knight, J. C., Amoroso, A. J., Edwards, P. G. & Ooi, L.-L. (2006). Acta Cryst. E62, m3306–m3308. Web of Science CSD CrossRef IUCr Journals Google Scholar
Robin, A. Y. & Fromm, K. M. (2006). Coord. Chem. Rev. 250, 2127–2157. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, H., Su, H., Xu, J., Bai, F. & Gao, Y. (2009). Acta Cryst. E65, m352–m353. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, C., Wang, Z., Gu, F. & Guo, G. (2010). J. Mol. Struct. 979, 92–100. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.